Olefin-based polymer

ABSTRACT

The present invention relates to an olefin-based polymer, which has (1) a density (d) ranging from 0.85 to 0.90 g/cc, (2) a melt index (MI, 190° C., 2.16 kg load conditions) ranging from 0.1 g/10 min to 15 g/10 min, (3) a molecular weight distribution (MWD) in a range of 1.0 to 3.0, and (4) a number average molecular weight (Mn) and a Z+1 average molecular weight (Mz+1) satisfying the Equation 1, {Mn/(Mz+1)}×100&gt;15. The olefin-based polymer according to the present invention is a low-density olefin-based polymer and exhibits excellent tensile strength due to having improved molecular weight as compared to the flow index.

CROSS-REFERENCE TO RELATED APPLICATION

The present application is a national phase entry under 35 U.S.C. § 371of International Application No. PCT/KR2018/016581 filed Dec. 24, 2018,which claims priority from Korean Patent Application No. 10-2017-0179658filed Dec. 26, 2017, all of which are incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to an olefin-based polymer, andspecifically, to a low-density olefin-based polymer having ahigh-molecular weight and an improved tensile strength.

BACKGROUND ART

Polyolefins are widely used for extrusion-molded articles, blow-moldedarticles and injection-molded articles due to excellent moldability,heat resistance, mechanical properties, hygienic quality, water vaporpermeability and appearance characteristics of molded articles thereof.However, polyolefins, particularly polyethylene, have a problem of lowcompatibility with polar resins such as nylon because of the absence ofpolar groups in the molecule, and low adhesiveness to polar resins andmetals. As a result, it is difficult to blend the polyolefin with polarresins or metals, or to laminate the polyolefin with these materials.Further, a molded article of a polyolefin has a problem of low surfacehydrophilicity and a low antistatic property.

In order to solve such a problem and to increase the affinity for apolar material, a method of grafting a polar group-containing monomeronto a polyolefin through radical polymerization has been widely used.However, this method has a problem in that cross-linking in themolecules of the polyolefin and cleavage of molecular chains occurduring the grafting reaction, and the viscosity balance of a graftpolymer and a polar resin is poor, and thus miscibility is low. There isalso a problem in that the appearance characteristics of a moldedarticle are low due to a gel component generated by intramolecularcrosslinking or a foreign substance generated by cleavage of molecularchains.

Further, as a method of preparing an olefin polymer such as an ethylenehomopolymer, an ethylene/α-olefin copolymer, a propylene homopolymer ora propylene/α-olefin copolymer, a method of copolymerizing a polarmonomer in the presence of a metal catalyst such as a titanium catalystor a vanadium catalyst was used. However, when the above-described metalcatalyst is used to copolymerize a polar monomer, there is a problemthat the molecular weight distribution or composition distribution iswide, and polymerization activity is low.

As another method, a method of polymerizing in the presence of ametallocene catalyst including a transition metal compound such aszircononocene dichloride and an organoaluminum oxy compound(aluminoxane) is known. When a metallocene catalyst is used, ahigh-molecular weight olefin polymer is obtained with high activity, andthe resulting olefin polymer has a narrow molecular weight distributionand a narrow composition distribution.

Further, as a method of preparing a polyolefin containing a polar groupusing a metallocene compound having a ligand of a non-crosslinkedcyclopentadienyl group, a crosslinked or non-crosslinked bisindenylgroup, or an ethylene crosslinked unsubstituted indenyl/fluorenyl groupas a catalyst, a method using a metallocene catalyst is also known.However, these methods have a disadvantage in that polymerizationactivity is very low. For this reason, a method of protecting a polargroup by a protecting group is carried out, but there is a problem thatthe process becomes complicated since a protecting group should beremoved again after the reaction when the protecting group isintroduced.

An ansa-metallocene compound is an organometallic compound containingtwo ligands connected to each other by a bridge group, in which therotation of the ligand is prevented and the activity and structure ofthe metal center are determined by the bridge group.

The ansa-metallocene compound is used as a catalyst in the preparationof olefin-based homopolymers or copolymers. In particular, it is knownthat an ansa-metallocene compound containing acyclopentadienyl-fluorenyl ligand can prepare a high-molecular weightpolyethylene, thereby controlling the microstructure of thepolypropylene.

Further, it is also known that an ansa-metallocene compound containingan indenyl ligand can produce a polyolefin having excellent activity andimproved stereoregularity.

As described above, various studies have been made on ansa-metallocenecompounds capable of controlling the microstructure of olefin-basedpolymers and having higher activity, but the research is stillinsufficient.

DISCLOSURE Technical Problem

An object of the present invention is to provide a low-densityolefin-based polymer having improved tensile strength due to anincreasing molecular weight.

Technical Solution

In order to achieve the object, the present invention provides anolefin-based polymer which has (1) a density (d) ranging from 0.85 to0.90 g/cc, (2) a melt index (MI, 190° C., 2.16 kg load conditions)ranging from 0.1 g/10 min to 15 g/10 min, (3) a molecular weightdistribution (MWD) in a range of 1.0 to 3.0, and (4) a number averagemolecular weight (Mn) and a Z+1 average molecular weight (Mz+1)satisfying the following Equation 1.{Mn/(Mz+1)}×100>15  [Equation 1]

Advantageous Effects

The olefin-based polymer according to the present invention is alow-density olefin-based polymer has an improved tensile strength due toan increasing molecular weight.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail toassist in the understanding of the present invention.

Terminology used in the specification and claims should not be construedas limited to conventional or literal meanings, and should be construedas having meanings and concepts corresponding to the technical idea ofthe present invention based on the principle that the inventor cansuitably define the concept of a term to explain his own invention inthe most preferable way.

In the specification, the term “a polymer” denotes a polymer compoundprepared by the polymerization of monomers having the same or differenttypes. The general term “the polymer” includes “a hybrid polymer” aswell as “a homopolymer,” “a copolymer” and “a terpolymer.” Further, “thehybrid polymer” denotes a polymer prepared by the polymerization of atleast two different types of monomers. The general term “the hybridpolymer” denotes “the copolymer” (commonly used for denoting a polymerprepared using two different types of monomers) and “the terpolymer”(commonly used for denoting a polymer prepared using three differenttypes of monomers). “The hybrid polymer” includes a polymer prepared bythe polymerization of at least four different types of monomers.

An olefin-based polymer according to the present invention satisfies thefollowing conditions of (1) to (4):

(1) a density (d) ranging from 0.85 g/cc to 0.90 g/cc, (2) a melt index(MI, 190° C., 2.16 kg load conditions) ranging from 0.1 g/10 min to 15g/10 min, (3) a molecular weight distribution (MWD) in a range of 1.0 to3.0, and (4) a number average molecular weight (Mn) and a Z+1 averagemolecular weight (Mz+1) satisfying the following Equation 1.{Mn/(Mz+1)}×100>15  [Equation 1]

Generally, the lower the density and the lower the hardness of thepolymer, the better the foaming. The olefin-based polymer according tothe present invention exhibits low hardness when it has a density of thesame level as that of conventional olefin-based polymers while having avery low density, and thus can exhibit more excellent foamability.

The olefin-based polymer according to the present invention exhibits alow density in the range of 0.85 g/cc to 0.90 g/cc when measured inaccordance with ASTM D-792, specifically in the range of 0.85 g/cc to0.89 g/cc, and more specifically in the range of 0.855 g/cc to 0.89g/cc. The olefin-based polymer according to the present inventionexhibits a low density in the above-described range, so that excellentfoamability can be exhibited.

(2) The melt index (MI) may be controlled by adjusting the amount of thecatalyst used in the polymerization of the olefin-based polymer withrespect to the comonomer, and affects the mechanical properties, impactstrength and moldability of the olefin-based polymer. In the presentspecification, the melt index is measured at 190° C. under a load of2.16 kg in accordance with ASTM D1238 at a low density of 0.85 g/cc to0.90 g/cc, and may be in the range of 0.1 g/10 min to 3 g/10 min,specifically, in the range of 0.2 g/10 min to 2 g/10 min, and morespecifically, in the range of 0.25 g/10 min to 1.8 g/10 min.

The olefin-based polymer according to the present invention has aultra-low density, and a high melt temperature and a high hardness whenthe olefin-based polymer has a density and a melt index of the samelevel as those of a conventional olefin-based polymer, and thus canexhibit superior tensile strength.

Further, The olefin-based polymer according to an embodiment of thepresent invention may have (3) a molecular weight distribution (MWD),which is a ratio (Mw/Mn) of a weight average molecular weight (Mw) to anumber average molecular weight (Mn), in the range of 1.0 to 3.0,specifically in the range of 1.5 to 3.0, and more specifically in therange of 1.8 to 3.0. The olefin-based polymer according to an embodimentof the present invention may exhibit a high molecular weight and anarrow molecular weight distribution.

Further, The olefin-based polymer according to an embodiment of thepresent invention may have (4) a number average molecular weight (Mn)and a Z+1 average molecular weight (Mz+1) satisfying the followingEquation 1.{Mn/(Mz+1)}×100>15  [Equation 1]

The olefin-based polymer according to an embodiment of the presentinvention has a value of 15 or more, which is obtained by dividing avalue of the number average molecular weight (Mn) by a value of z+1average molecular weight (Mz+1) and multiplied it by 100. Theolefin-based polymer according to the present invention has a highernumber average molecular weight (Mn) when it has a z+1 average molecularweight (Mz+1) of the same level as that of conventional olefin-basedpolymers.

Mn, Mw and Mz+1 are defined as follows.

$M_{n\;} = \frac{\sum{N_{i}M_{i}}}{\sum N_{i}}$$M = \frac{\sum{N_{i}M_{i}^{n + 1}}}{\sum{N_{i}M_{i}^{n}}}$

When n=1, M=Mw, and when n=3, M=Mz+1.

Mn is the number average molecular weight; Mw is the weight averagemolecular weight; and Mz+1 is the Z+1 average molecular weight. All areterms referring to the average molecular weight.

The olefin-based polymer according to an embodiment of the presentinvention may have (5) a weight average molecular weight (Mw) in therange of 10,000 g/mol to 500,000 g/mol, specifically in the range of20,000 g/mol to 300,000 g/mol, and more specifically in the range of50,000 g/mol to 200,000 g/mol.

Further, the olefin-based polymer according to an embodiment of thepresent invention may have (6) a number average molecular weight (Mn) inthe range of 8,000 g/mol to 300,000 g/mol, specifically in the range of10,000 g/mol to 200,000 g/mol, and more specifically in the range of20,000 g/mol to 80,000 g/mol.

In the present invention, the weight average molecular weight (Mw) andthe number average molecular weight (Mn) are a polystyrene-convertedmolecular weight which is analyzed by gel permeation chromatography(GPC).

Further, the olefin-based polymer according to an embodiment of thepresent invention has (7) a Z+1 average molecular weight (Mz+1) in arange of 50,000 g/mol to 1,500,000 g/mol, specifically in the range of80,000 g/mol to 1,000,000 g/mol, and more specifically in the range of100,000 g/mol to 900,000 g/mol. When the olefin-based polymer satisfiesthe Z+1 average molecular weight (Mz+1) in the above range, it exhibitsexcellent hardness due to including an appropriate high molecular weightcomponent, and can exhibit an improved tensile strength.

Generally, the density of the olefin-based polymer is affected by thetype and content of the monomers used in the polymerization, the degreeof polymerization and the like, and the copolymer is highly affected bythe content of the comonomer. The olefin-based polymer of the presentinvention is polymerized using a catalyst composition containing twotypes of transition metal compounds having a characteristic structure,and a large amount of comonomers may be introduced, and the olefin-basedpolymer of the present invention has a low density in the range asdescribed above.

Specifically, when the olefin-based polymer according to an embodimentof the present invention, which is a copolymer of ethylene and 1-butene,satisfies the density in the range of 0.855 g/cc to 0.870 g/cc and themelt index (MI) in the range of 0.1 g/10 min to 2 g/10 min, theolefin-based polymer may satisfy in a range of 10,000 g/mol to 500,000g/mol, specifically in the range of 20,000 g/mol to 300,000 g/mol, andmore specifically in the range of 50,000 g/mol to 200,000 g/mol.Further, when the olefin-based polymer satisfies a density in the rangeof 0.855 g/cc to 0.865 g/cc and a melt index (MI) in the range of 0.1g/10 min to 2 g/10 min, a tensile strength at break measured inaccordance with ASTM D638 may be in the range of 10 to 200,specifically, in the range of 15 to 170.

Further, the olefin-based polymer according to an embodiment of thepresent invention may have (8) I₁₀/I₂>7.91(MI_(2.16))^(−0.188). The I₁₀and I_(2.16) represent a melt index (MI), measured in accordance withASTM D-1238, and may be used as a marker of a molecular weight.

The olefin-based polymer is a homopolymer or two or more copolymersselected from an olefin-based monomer, specifically, analpha-olefin-based monomer, a cyclic olefin-based monomer, a dieneolefin-based monomer, a triene olefin-based monomer, and a styrene-basedmonomer. More specifically, the olefin-based polymer may be a copolymerof ethylene and an alpha-olefin having 3 to 12 carbon atoms or 3 to 10carbon atoms.

The alpha-olefin comonomer may include any one or a mixture of two ormore selected from the group consisting of propylene, 1-butene,1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene,1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene,norbornene, norbornadiene, ethylidene norbornene, phenyl norbornene,vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene,1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and3-chloromethyl styrene.

More specifically, the olefin copolymer according to an embodiment ofthe present invention may be a copolymer of ethylene and propylene,ethylene and 1-butene, ethylene and 1-hexene, ethylene and4-methyl-1-pentene or ethylene and 1-octene.

When the olefin-based polymer is a copolymer of ethylene and analpha-olefin, the amount of the alpha-olefin may be 80 wt % or less,more specifically 60 wt % or less, still more specifically in the rangeof 5 wt % to 40 wt % with respect to a total weight of the copolymer.

When the alpha-olefin is included in the above-described range, it iseasy to realize the above-mentioned physical properties.

The olefin-based polymer according to an embodiment of the presentinvention, which has the above-described physical properties andconstitutional characteristics may be prepared by a continuous solutionpolymerization reaction in the presence of a metallocene catalystcomposition including at least one type of a transition metal compoundin a single reactor. Accordingly, in the olefin-based polymer accordingto an embodiment of the present invention, a block formed by linearlyconnecting two or more repeating units derived from one monomer amongmonomers constituting a polymer in the polymer is not formed. That is,the olefin-based polymer according to the present invention does notinclude a block copolymer, but may be selected from the group consistingof a random copolymer, an alternating copolymer and a graft copolymer,more particularly, may be a random copolymer.

Specifically, the olefin-based polymer of the present invention may beobtained by a preparation method including a step of polymerizing anolefin-based monomer in the presence of a catalyst composition forolefin polymerization including a transition metal compound representedby the following Formula 1.

However, in the preparation of an olefin-based polymer according to anembodiment of the present invention, the structure range of transitionmetal compound 1 is not limited to specifically disclosed types, and allmodifications, equivalents, or replacements included in the scope andtechnical range of the present invention should be understood to beincluded in the present invention.

In Formula 1,

R₁ is hydrogen; an alkyl having 1 to 20 carbon atoms; a cycloalkylhaving 3 to 20 carbon atoms; an alkenyl having 2 to 20 carbon atoms; analkoxy having 1 to 20 carbon atoms; an aryl having 6 to 20 carbon atoms;an arylalkoxy having 7 to 20 carbon atoms; an alkylaryl having 7 to 20carbon atoms; or an arylalkyl having 7 to 20 carbon atoms,

R_(2a) to R_(2e) each independently represent hydrogen; a halogen; analkyl having 1 to 20 carbon atoms; a cycloalkyl having 3 to 20 carbonatoms; an alkenyl having 2 to 20 carbon atoms; an alkoxy having 1 to 20carbon atoms; or an aryl having 6 to 20 carbon atoms,

R₃ is hydrogen; a halogen; an alkyl having 1 to 20 carbon atoms; acycloalkyl having 3 to 20 carbon atoms; an alkenyl having 2 to 20 carbonatoms; an aryl having 6 to 20 carbon atoms; an alkylaryl having 7 to 20carbon atoms; an arylalkyl having 7 to 20 carbon atoms; an alkylamidohaving 1 to 20 carbon atoms; an arylamido having 6 to 20 carbon atoms;an alkylidene having 1 to 20 carbon atoms; or phenyl substituted withone or more selected from the group consisting of a halogen, an alkylhaving 1 to 20 carbon atoms, a cycloalkyl having 3 to 20 carbon atoms,an alkenyl having 2 to 20 carbon atoms, an alkoxy having 1 to 20 carbonatoms, and an aryl having 6 to 20 carbon atoms,

R₄ to R₉ each independently represent hydrogen; a silyl; an alkyl having1 to 20 carbon atoms; a cycloalkyl having 3 to 20 carbon atoms; analkenyl having 2 to 20 carbon atoms; an aryl having 6 to 20 carbonatoms; an alkylaryl having 7 to 20 carbon atoms; an arylalkyl having 7to 20 carbon atoms; or a metalloid radical of a Group 14 metalsubstituted with a hydrocarbyl having 1 to 20 carbon atoms; two or moreadjacent ones of R₆ to R₉ may be connected to each other to form a ring,

Q is Si, C, N, P or S,

M is a Group 4 transition metal,

X₁ and X₂ are each independently hydrogen; a halogen; an alkyl having 1to 20 carbon atoms; a cycloalkyl having 3 to 20 carbon atoms; an alkenylhaving 2 to 20 carbon atoms; an aryl having 6 to 20 carbon atoms; analkylaryl having 7 to 20 carbon atoms; an arylalkyl having 7 to 20carbon atoms; an alkylamino having 1 to 20 carbon atoms; an arylaminohaving 6 to 20 carbon atoms; or an alkylidene having 1 to 20 carbonatoms.

According to an embodiment of the present invention, in the transitionmetal compound represented by Formula 1,

R₁ may be hydrogen; an alkyl having 1 to 20 carbon atoms; a cycloalkylhaving 3 to 20 carbon atoms; an alkoxy having 1 to 20 carbon atoms; anaryl having 6 to 20 carbon atoms; an arylalkoxy having 7 to 20 carbonatoms; an alkylaryl having 7 to 20 carbon atoms; or an arylalkyl having7 to 20 carbon atoms,

R_(2a) to R_(2e) each may independently represent hydrogen; a halogen;an alkyl having 1 to 12 carbon atoms; a cycloalkyl having 3 to 12 carbonatoms; an alkenyl having 2 to 12 carbon atoms; an alkoxy having 1 to 12carbon atoms; or phenyl,

R₃ may be hydrogen; a halogen; an alkyl having 1 to 12 carbon atoms; acycloalkyl having 3 to 12 carbon atoms; an alkenyl having 2 to 12 carbonatoms; an aryl having 6 to 20 carbon atoms; an alkylaryl having 7 to 13carbon atoms; an arylalkyl having 7 to 13 carbon atoms; or phenylsubstituted with one or more selected from the group consisting of ahalogen, an alkyl having 1 to 12 carbon atoms, a cycloalkyl having 3 to12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, an alkoxyhaving 1 to 12 carbon atoms and phenyl,

R₄ to R₉ each may independently represent hydrogen; an alkyl having 1 to20 carbon atoms; a cycloalkyl having 3 to 20 carbon atoms; an arylhaving 6 to 20 carbon atoms; an alkylaryl having 7 to 20 carbon atoms;or an arylalkyl having 7 to 20 carbon atoms,

two or more adjacent ones of R₆ to R₉ may be connected to each other toform an aliphatic ring having 5 to 20 carbon atoms or an aromatic ringhaving 6 to 20 carbon atoms; the aliphatic ring or aromatic ring may besubstituted with a halogen, an alkyl having 1 to 20 carbon atoms, analkenyl having 2 to 12 carbon atoms, or an aryl having 6 to 12 carbonatoms,

Q may be Si,

M may be Ti,

X₁ and X₂ each may independently represent hydrogen; a halogen; an alkylhaving 1 to 12 carbon atoms; a cycloalkyl having 3 to 12 carbon atoms;an alkenyl having 2 to 12 carbon atoms; an aryl having 6 to 12 carbonatoms; an alkylaryl having 7 to 13 carbon atoms; an arylalkyl having 7to 13 carbon atoms; an alkylamino having 1 to 13 carbon atoms; anarylamino having 6 to 12 carbon atoms; or an alkylidene having 1 to 12carbon atoms.

According to another embodiment of the present invention, in thetransition metal compound represented by Formula 1,

R₁ may be hydrogen; an alkyl having 1 to 12 carbon atoms; a cycloalkylhaving 3 to 12 carbon atoms; an alkoxy having 1 to 12 carbon atoms; anaryl having 6 to 12 carbon atoms; an arylalkoxy having 7 to 13 carbonatoms; an alkylaryl having 7 to 13 carbon atoms; or an arylalkyl having7 to 13 carbon atoms,

R_(2a) to R_(2e) each may independently represent hydrogen; a halogen;an alkyl having 1 to 12 carbon atoms; a cycloalkyl having 3 to 12 carbonatoms; an alkenyl having 2 to 12 carbon atoms; an alkoxy having 1 to 12carbon atoms; or phenyl,

R₃ may be hydrogen; a halogen; an alkyl having 1 to 12 carbon atoms; acycloalkyl having 3 to 12 carbon atoms; an alkenyl having 2 to 12 carbonatoms; an alkylaryl having 7 to 13 carbon atoms; an arylalkyl having 7to 13 carbon atoms; phenyl; or phenyl substituted with one or moreselected from the group consisting of a halogen, an alkyl having 1 to 12carbon atoms, a cycloalkyl having 3 to 12 carbon atoms, an alkenylhaving 2 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms andphenyl,

R₄ to R₉ each may independently represent hydrogen; an alkyl having 1 to12 carbon atoms; a cycloalkyl having 3 to 12 carbon atoms; an arylhaving 6 to 12 carbon atoms; an alkylaryl having 7 to 13 carbon atoms;or an arylalkyl having 7 to 13 carbon atoms,

two or more adjacent ones of R₆ to R₉ may be connected to each other toform an aliphatic ring having 5 to 12 carbon atoms or an aromatic ringhaving 6 to 12 carbon atoms;

the aliphatic or aromatic ring may be substituted with a halogen, analkyl having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or anaryl having 6 to 12 carbons,

Q may be Si,

M may be Ti,

X₁ and X₂ each may independently represent hydrogen; a halogen; an alkylgroup having 1 to 12 carbon atoms; or an alkenyl having 2 to 12 carbonatoms.

Further, according to still another embodiment of the present invention,in the transition metal compound represented by Formula 1,

R₁ may be hydrogen or an alkyl having 1 to 12 carbon atoms,

R_(2a) to R_(2e) each may independently represent hydrogen; an alkylhaving 1 to 12 carbon atoms; or an alkoxy having 1 to 12 carbon atoms,

R₃ may be hydrogen; an alkyl having 1 to 12 carbon atoms; or phenyl,

R₄ and R₅ each may independently represent hydrogen; or an alkyl having1 to 12 carbon atoms,

R₆ to R₉ each may independently represent hydrogen or methyl,

Q may be Si,

M may be Ti,

X₁ and X₂ each may independently represent hydrogen or an alkyl having 1to 12 carbon atoms.

The compound represented by Formula 1 may specifically be any one of thecompounds represented by the following Formulas 1-1 to 1-10.

In addition, it may be a compound having various structures within theranges defined in Formula 1.

Further, in the transition metal compound represented by Formula 1, ametal site is connected by a cyclopentadienyl ligand to whichbenzothiophene is fused, and the structure thereof has a narrow Cp-M-Nangle and a wide X₁-M-X₂ angle to which a monomer approaches. Inaddition, the benzothiophene fused cyclopentadienyl ligand, Si, nitrogenand the metal site are connected in order via the bonding of a ringshape to form a more stable and rigid pentagonal ring structure.Therefore, when these compounds are activated by reacting with acocatalyst such as methylaluminoxane or B(C₆F₅)₃ and then applied toolefin polymerization, an olefin-based polymer having characteristicssuch as high activity, high molecular weight, high copolymerizationproperties and the like may be polymerized even at a high polymerizationtemperature.

Each of the substituents defined in the present specification will bedescribed in detail as follows.

In the present specification, unless particularly defined otherwise, a“hydrocarbyl group” means a monovalent hydrocarbon group having 1 to 20carbon atoms formed only with carbon and hydrogen regardless of itsstructure such as an alkyl group, an aryl group, an alkenyl group, analkinyl group, a cycloalkyl group, an alkylaryl group and an arylalkylgroup.

The term “halogen” used in the present specification, unless otherwisespecified, refers to fluorine, chlorine, bromine and iodine.

The term “alkyl” used in the present specification, unless otherwisespecified, refers to a linear or branched hydrocarbon residue.

The term “alkenyl” used in the present specification, unless otherwisespecified, refers to a linear or branched alkenyl group.

The branched chain may be an alkyl having 1 to 20 carbon atoms; analkenyl having 2 to 20 carbon atoms; an aryl having 6 to 20 carbonatoms; an alkylaryl having 7 to 20 carbon atoms; or an arylalkyl having7 to 20 carbon atoms.

According to an embodiment of the present invention, the aryl grouppreferably has 6 to 20 carbon atoms, and specifically includes phenyl,naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl and the like,but is not limited thereto.

The alkylaryl group refers to an aryl group substituted with the alkylgroup.

The arylalkyl group refers to an alkyl group substituted with the arylgroup.

The ring (or a heterocyclic group) refers to a monovalent aliphatic oraromatic hydrocarbon group which has a ring atom with 5 to 20 carbonatoms and contains one or more heteroatoms, and may be a single ring ora condensed ring of two or more rings. Further, the heterocyclic groupmay be unsubstituted or substituted with an alkyl group. Examplesthereof include indoline, tetrahydroquinoline and the like, but thepresent invention is not limited thereto.

The alkylamino group refers to an amino group substituted with the alkylgroup, and includes a dimethylamino group, a diethylamino group and thelike, but is not limited thereto.

According to an embodiment of the present invention, the aryl grouppreferably has 6 to 20 carbon atoms, and specifically includes phenyl,naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl and the like,but is not limited thereto.

The transition metal compound of Formula 1 and a ligand compound ofFormula 2 allow introduction of a large amount of an alpha-olefin aswell as low-density polyethylene due to the structural characteristicsof the catalyst, and thus it is possible to prepare a low-densitypolyolefin copolymer having a density in the range of 0.85 to 0.90 g/cc,specifically, in the range of 0.85 g/cc to 0.89 g/cc, and morespecifically, in the range of 0.855 g/cc to 0.89 g/cc.

The transition metal compound of Formula 1 may be prepared from a ligandcompound represented by the following Formula 2.

In Formula 2,

R₁ and R₁₀ each independently represent hydrogen; an alkyl having 1 to20 carbon atoms; a cycloalkyl having 3 to 20 carbon atoms; an alkenylhaving 2 to 20 carbon atoms; an alkoxy having 1 to 20 carbon atoms; anaryl having 6 to 20 carbon atoms; an arylalkoxy having 7 to 20 carbonatoms; an alkylaryl having 7 to 20 carbon atoms; or an arylalkyl having7 to 20 carbon atoms,

R_(2a) to R_(2e) each independently represent hydrogen; a halogen; analkyl having 1 to 20 carbon atoms; a cycloalkyl having 3 to 20 carbonatoms; an alkenyl having 2 to 20 carbon atoms; an alkoxy having 1 to 20carbon atoms; or an aryl having 6 to 20 carbon atoms,

R₃ is hydrogen; a halogen; an alkyl having 1 to 20 carbon atoms; acycloalkyl having 3 to 20 carbon atoms; an alkenyl having 2 to 20 carbonatoms; an aryl having 6 to 20 carbon atoms; an alkylaryl having 6 to 20carbon atoms; an arylalkyl having 7 to 20 carbon atoms; an alkylamidohaving 1 to 20 carbon atoms; an arylamido having 6 to 20 carbon atoms;an alkylidene having 1 to 20 carbon atoms; or phenyl substituted withone or more selected from the group consisting of a halogen, an alkylhaving 1 to 20 carbon atoms, a cycloalkyl having 3 to 20 carbon atoms,an alkenyl having 2 to 20 carbon atoms, an alkoxy having 1 to 20 carbonatoms, and an aryl having 6 to 20 carbon atoms,

R₄ to R₉ each independently represent hydrogen; a silyl;

an alkyl having 1 to 20 carbon atoms; a cycloalkyl having 3 to 20 carbonatoms; an alkenyl having 2 to 20 carbon atoms; an aryl having 6 to 20carbon atoms; an alkylaryl having 7 to 20 carbon atoms; an arylalkylhaving 7 to 20 carbon atoms; or a metalloid radical of a Group 14 metalsubstituted with a hydrocarbyl having 1 to 20 carbon atoms; and two ormore adjacent ones of R₆ to R₉ may be connected to each other to form aring,

Q is Si, C, N, P or S.

In the ligand compound, the definitions of R₁ to R₉ in the compoundrepresented by Formula 2 may be the same as those in the compoundrepresented by Formula 1, which is a transition metal compound.

The compound represented by Formula 2 may specifically be any one of thecompounds represented by Formulas 2-1 to 2-10.

The ligand compound represented by Formula 2 of the present inventionmay be prepared as shown in the following Reaction Scheme 1.

In Reaction Scheme 1, R₁ to R₁₀ and Q are the same as defined in Formula2.

Specifically, a method of preparing a ligand compound of Formula 2 mayinclude steps of a) reacting a compound represented by the followingFormula 4 with a compound represented by the following Formula 5 toprepare a compound represented by the following Formula 3; and b)reacting a compound represented by the following Formula 3 with acompound represented by the following Formula 6 to prepare a compoundrepresented by the following Formula 2.

In the Formulae, R₁ to R₁₀ and Q are the same as defined in Formula 2.

In Step a) of reacting a compound represented by the following Formula 4with a compound represented by the following Formula 5 to prepare acompound represented by the following Formula 3, the compoundrepresented by Formula 4 and the compound represented by Formula 5 maybe reacted in a molar ratio of 1:0.8 to 1:5.0, specifically 1:0.9 to1:4.0, and more specifically, 1:1 to 1:3.0.

Further, the reaction may be carried out at a temperature ranging from−80° C. to 140° C. for 1 hour to 48 hours.

Further, in Step b) of reacting a compound represented by the followingFormula 3 with a compound represented by the following Formula 6 toprepare a compound represented by the following Formula 2, the compoundrepresented by Formula 3 and the compound represented by Formula 6 maybe reacted in a molar ratio of 1:0.8 to 1:5.0, specifically 1:0.9 to1:4.5, and more specifically, 1:1 to 1:4.0.

The compound represented by Formula 4 may be prepared as shown inReaction Scheme 2.

In Reaction Scheme 2, R₄ to R₉ are the same as defined in Formula 1 orFormula 2.

The transition metal compound represented by Formula 1 of the presentinvention may be prepared by using the ligand compound represented byFormula 2 as shown in the following Reaction Scheme 3.

In the Formulas, R₁ to R₁₀, Q, M, X₁ and X₂ are the same as defined inFormula 1 or Formula 2.

According to an embodiment of the present invention, the transitionmetal compound represented by Formula 1 may be a compound in which aGroup 4 transition metal is coordinated to the compound represented byFormula 2 as a ligand.

Specifically, as shown in Reaction Scheme 3, the compound represented byFormula 2 is reacted with a compound represented by Formula 7, which isa metal precursor, and an organolithium compound, and thus thetransition metal compound of Formula 1 in which a Group 4 transitionmetal is coordinated to the compound represented by Formula 2 as aligand may be obtained.

In the Formulas, R₁ to R₁₀, Q, M, X₁ and X₂ are the same as defined inFormula 1.

In Reaction Scheme 3, the organolithium compound may be one or moreselected from the group consisting of n-butyl lithium, sec-butyllithium, methyl lithium, ethyl lithium, isopropyl lithium, cyclohexyllithium, allyl lithium, vinyl lithium, phenyl lithium and benzyllithium.

The compound represented by Formula 2 and the compound represented byFormula 7 may be mixed in a molar ratio of 1:0.8 to 1:1.5, andpreferably 1:1.0 to 1:1.1.

Further, the organolithium compound may be used in an amount of 180 to250 parts by weight based on 100 parts by weight of the compoundrepresented by Formula 2.

The reaction may be carried out at a temperature in the range of −80° C.to 140° C. for 1 hour to 48 hours.

The transition metal compound of Formula 1 may be used alone or incombination including one or more cocatalyst compounds represented bythe following Formula 8, Formula 9 and Formula 10 in addition to thetransition metal compound of Formula 1 as a catalyst for thepolymerization reaction.—[Al(R₁₁)—O]_(a)—  [Formula 8]A(R₁₁)₃  [Formula 9][L-H]⁺[W(D)₄]⁻ or [L]⁺[W(D)₄]⁻  [Formula 10]

In Formulae 8 to 10,

R₁₁ may be the same or different, and each independently selected fromthe group consisting of a halogen, a hydrocarbyl having 1 to 20 carbonatoms, and a hydrocarbyl having 1 to 20 carbon atoms substituted with ahalogen,

A is aluminum or boron,

D is independently an aryl having 6 to 20 carbon atoms or an alkylhaving 1 to 20 carbon atoms in which at least one hydrogen atom may besubstituted with a substituent, and here, the substituent is at leastany one selected from the group consisting of a halogen, a hydrocarbylhaving 1 to 20 carbon atoms, an alkoxy having 1 to 20 carbon atoms, andan aryloxy having 6 to 20 carbon atoms,

H is a hydrogen atom,

L is a neutral or cationic Lewis acid,

W is a Group 13 element,

a is an integer of 2 or more.

Examples of the compound represented by Formula 8 includealkylaluminoxanes such as methylaluminoxane (MAO), ethylaluminoxane,isobutylaluminoxane, butylaluminoxane and the like, and modified alkylaluminoxanes having two or more of the alkylaluminoxanes mixed therein,and specifically may be methyl aluminoxane and modified methylaluminoxane (MAO).

Examples of the compound represented by Formula 9 includetrimethylaluminum, triethylaluminum, triisobutylaluminum,tripropylaluminum, tributylaluminum, dimethylchloroaluminum,tri-iso-propyl aluminum, tri-sec-butyl aluminum, tricyclopentylaluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum,trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum,triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide,dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutylboron, tripropyl boron, tributyl boron and the like, and specifically,may be selected from trimethyl aluminum, triethyl aluminum andtriisobutyl aluminum.

Examples of the compound represented by Formula 10 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron,trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron,trimethylammonium tetra(p-tolyl) boron, trimethylammoniumtetra(o,p-dimethylphenyl) boron, tributylammoniumtetra(p-trifluoromethylphenyl) boron, trimethylammoniumtetra(p-trifluoromethylphenyl) boron, tributylammoniumtetrapentafluorophenylboron, N,N-diethylanilinium tetraphenylboron,N,N-diethylanilinium tetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron,trimethylphosphonium tetraphenylboron, dimethylaniliniumtetrakis(pentafluorophenyl) borate, triethylammonium tetraphenylaluminum, tributylammonium tetraphenyl aluminum, trimethylammoniumtetraphenyl aluminum, tripropylammonium tetraphenyl aluminum,trimethylammonium tetra(p-tolyl) aluminum, tripropylammoniumtetra(p-tolyl) aluminum, triethylammoniumtetra (o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl) aluminum,trimethylammonium tetra(p-trifluoromethylphenyl) aluminum,tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylaniliniumtetraphenyl aluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentafluorophenyl aluminum,triphenylphosphonium tetraphenyl aluminum, trimethylphosphoniumtetraphenyl aluminum, tripropylammonium tetra(p-tolyl) boron,triethylammonium tetra(o,p-dimethylphenyl) boron, triphenylcarboniumtetra(p-trifluoromethylphenyl) boron, triphenylcarboniumtetrapentafluorophenylboron and the like.

The catalyst composition may be prepared by a method including 1)bringing a transition metal compound represented by Formula 1 intocontact with a compound represented by Formula 8 or 9 to obtain amixture; and 2) adding a compound represented by Formula 10 to themixture, as the first method.

Further, the catalyst composition may be prepared by a method ofbringing a transition metal compound represented by Formula 1 intocontact with a compound represented by Formula 8, as the second method.

In the first method among the above-described preparation methods of thecatalyst composition, the molar ratio of the transition metal compoundrepresented by Formula 1/the compound represented by Formula 8 or 9 maybe in the range of 1/5,000 to 1/2, specifically in the range of 1/1000to 1/10, and more specifically in the range of 1/500 to 1/20. When themolar ratio of the transition metal compound represented by Formula1/the compound represented by Formula 8 or 9 exceeds 1/2, the amount ofthe alkylating agent is very small, and thus the alkylation of the metalcompound is not fully carried out. When the molar ratio is less than1/5000, the alkylation of the metal compound is carried out, but theactivation of the alkylated metal compound is not fully achieved due tothe side reaction between the remaining excess alkylating agent and theactivating agent which is a compound of Formula 10. Further, the molarratio of the transition metal compound represented by Formula 1/thecompound represented by Formula 10 may be in the range of 1/25 to 1,specifically in the range of 1/10 to 1, and more specifically in therange of 1/5 to 1. When the molar ratio of the transition metal compoundrepresented by Formula 1/the compound represented by Formula 10 is morethan 1, the amount of the activator is relatively small, so that themetal compound is not fully activated, and thus the activity of theresulting catalyst composition may be lowered. When the molar ratio isless than 1/25, the activation of the metal compound is fully performed,but the unit cost of the catalyst composition may not be economical dueto the remaining excess activator, or the purity of the produced polymermay be lowered.

In the second method among the above-described preparation methods ofthe catalyst composition, the molar ratio of the transition metalcompound represented by Formula 1/the compound represented by Formula 8may be in the range of 1/10,000 to 1/10, and specifically in the rangeof 1/5,000 to 1/100, and more specifically in the range of 1/3,000 to1/500. When the molar ratio is more than 1/10, the amount of theactivator is relatively small, so that the activation of the metalcompound is not fully achieved, and thus the activity of the resultingcatalyst composition may be lowered. When the molar ratio is less than1/10,000, the activation of the metal compound is fully performed, butthe unit cost of the catalyst composition may not be economical due tothe remaining excess activator, or the purity of the produced polymermay be lowered.

In the preparation of the catalyst composition, a hydrocarbon-basedsolvent such as pentane, hexane, heptane or the like, or an aromaticsolvent such as benzene, toluene or the like may be used as a reactionsolvent.

Further, the catalyst composition may include the transition metalcompound and a cocatalyst compound in the form of being supported on acarrier.

The carrier may be used without any particular limitation as long as itis used as a carrier in a metallocene catalyst. Specifically, thecarrier may be silica, silica-alumina, silica-magnesia or the like, andany one or a mixture of two or more thereof may be used.

In the case where the support is silica, there are few catalystsliberated from the surface during the olefin polymerization processsince the silica carrier and the functional groups of the metallocenecompound of Formula 1 form a chemical bond. As a result, it is possibleto prevent the occurrence of fouling of the wall surface of the reactoror the polymer particles entangled with each other during thepreparation process of the olefin-based polymer. Further, theolefin-based polymer prepared in the presence of the catalyst containingthe silica carrier has an excellent particle shape and apparent densityof the polymer.

More specifically, the carrier may be high-temperature dried silica orsilica-alumina containing a siloxane group having high reactivity on thesurface through a method such as high-temperature drying.

The carrier may further include an oxide, carbonate, sulfate or nitratecomponent such as Na₂O, K₂CO₃, BaSO₄, Mg(NO₃)₂ or the like.

The polymerization reaction for polymerizing the olefin-based monomermay be carried out by a conventional process applied to thepolymerization of olefin monomers such as continuous solutionpolymerization, bulk polymerization, suspension polymerization, slurrypolymerization, emulsion polymerization or the like.

The polymerization reaction of olefin monomers may be carried out in thepresence of an inert solvent, and examples of the inert solvent includebenzene, toluene, xylene, cumene, heptane, cyclohexane,methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene and 1-octene,but the present invention is not limited thereto.

The polymerization of the olefin-based polymer may be carried out byreacting at a temperature of about 25° C. to about 500° C. and apressure of about 1 kgf/cm² to about 100 kgf/cm².

Specifically, the polymerization of the polyolefin may be carried out ata temperature of from about 25° C. to about 500° C., and specifically ata temperature in the range of 80° C. to 250° C., and more preferably inthe range of 100° C. to 200° C. Further, the reaction pressure at thetime of polymerization may be in the range of 1 kgf/cm² to 150 kgf/cm²,preferably 1 kgf/cm² to 120 kgf/cm², and more preferably 5 kgf/cm² to100 kgf/cm².

Due to having improved physical properties, the olefin-based polymer ofthe present invention may be used for blow molding, extrusion molding orinjection molding in diverse fields and uses including wrapping,construction, daily supplies, or the like, such as a material of anautomobile, a wire, a toy, a fiber, a medicine, or the like.Particularly, the olefin-based polymer may be used for an automobilewhich requires excellent impact strength.

Further, the olefin-based polymer of the present invention may beusefully used in the production of molded articles.

The molded article may particularly include a blow molded article, aninflation molded article, a cast molded article, an extrusion laminatemolded article, an extrusion molded article, a foamed molded article, aninjection molded article, a sheet, a film, a fiber, a monofilament, anon-woven fabric, or the like.

MODE FOR CARRYING OUT THE INVENTION Examples

Hereinafter, the present invention will be explained in particular withreference to the following examples. However, the following examples areillustrated to assist the understanding of the present invention, andthe scope of the present invention is not limited thereto.

Preparation Example 1: Preparation of Transition Metal Compound 1

Synthesis ofN-tert-butyl-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(phenyl) silane amine of Formula 2-4

Preparation ofchloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(phenyl) silane

10 g (1.0 eq, 49.925 mmol) of 1,2-dimethyl-3H-benzo[b] cyclopenta[d]thiophene and 100 ml of THF were put into a 250 ml Schlenk flask, and 22ml of n-BuLi (1.1 eq, 54.918 mmol, 2.5 M in hexane) was added dropwiseat −30° C., followed by stirring at room temperature for 3 hours. Thestirred Li-complex THF solution was cannulated at −78° C. to a Schlenkflask containing 8.1 ml (1.0 eq, 49.925 mmol) of dichloro(methyl)(phenyl)silane and 70 ml of THF, and stirred overnight at roomtemperature. After stirring and vacuum drying, a mixture was extractedwith 100 ml of hexane.

Preparation ofN-tert-butyl-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(phenyl)silane amine

42 ml (8 eq, 399.4 mmol) of t-BuNH₂ was introduced into 100 ml of theextractedchloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen3-yl)-1,1-(methyl)(phenyl)silane hexane solution at room temperature, followed by stirringovernight at room temperature. After stirring and vacuum drying, amixture was extracted using 150 ml of hexane. After drying the solvent,13.36 g (68%, dr=1:1) of a yellow solid was obtained.

¹H NMR (CDCl₃, 500 MHz): δ 7.93 (t, 2H), 7.79 (d, 1H), 7.71 (d, 1H),7.60 (d, 2H), 7.48 (d, 2H), 7.40˜7.10 (m, 10H, aromatic), 3.62 (s, 1H),3.60 (s, 1H), 2.28 (s, 6H), 2.09 (s, 3H), 1.76 (s, 3H), 1.12 (s, 18H),0.23 (s, 3H), 0.13 (s, 3H)

<Synthesis of Transition of Metal Compound 1>

4.93 g (12.575 mmol, 1.0 eq) of the ligand compound of Formula 2-4 and50 ml (0.2 M) of toluene were put into a 100 ml Schlenk flask, and 10.3ml (25.779 mmol, 2.05 eq, 2.5 M in hexane) of n-BuLi was added dropwiseat −30° C., followed by stirring at room temperature overnight. Afterstirring, 12.6 ml (37.725 mmol, 3.0 eq., 3.0 M in diethyl ether) ofMeMgBr was added dropwise, and then 13.2 ml (13.204 mmol, 1.05 eq, 1.0 Min toluene) of TiCl₄ was added and stirred overnight at roomtemperature. After stirring and vacuum drying, the mixture was extractedwith 150 ml of hexane, and the solvent was removed to 50 ml. 4 ml(37.725 mmol, 3.0 eq) of DME was added dropwise thereto, followed bystirring at room temperature overnight. After vacuum drying again, amixture was extracted with 150 ml of hexane. After drying the solvent,2.23 g (38%, dr=1:0.5) of a brown solid was obtained.

¹H NMR (CDCl₃, 500 MHz): δ 7.98 (d, 1H), 7.94 (d, 1H), 7.71 (t, 6H),7.50˜7.30 (10H), 2.66 (s, 3H), 2.61 (s, 3H), 2.15 (s, 3H), 1.62 (s, 9H),1.56 (s, 9H), 1.53 (s, 3H), 0.93 (s, 3H), 0.31 (s, 3H), 0.58 (s, 3H),0.51 (s, 3H), −0.26 (s, 3H), −0.39 (s, 3H)

Preparation Example 2: Preparation of Transition Metal Compound 2

(1) Preparation of(8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline)(i) Preparation of Lithium Carbamate

1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150mL) were put into a Schlenk flask. The Schlenk flask was immersed in a−78° C. low temperature bath formed of dry ice and acetone, and stirredfor 30 minutes. Subsequently, n-BuLi (39.3 mL, 2.5 M, 98.24 mmol) wasadded via a syringe under a nitrogen atmosphere, and a pale yellowslurry was formed. Then, after the flask was stirred for 2 hours, thetemperature of the flask was raised to room temperature while removingthe produced butane gas. The flask was immersed again in alow-temperature bath at −78° C., the temperature was lowered, and thenCO₂ gas was introduced. As the carbon dioxide gas was introduced, theslurry disappeared and became a clear solution. The flask was connectedto a bubbler to remove the carbon dioxide gas, and a temperature wasraised to room temperature. Thereafter, an excess amount of CO₂ gas anda solvent were removed under vacuum. The flask was transferred to a drybox, and pentane was added thereto, followed by vigorous stirring andfiltration to obtain lithium carbamate which is a white solid compound.The white solid compound was coordinated with diethyl ether. The yieldwas 100%.

¹H NMR (C₆D₆, C₅D₅N): δ 1.90 (t, J=7.2 Hz, 6H, ether), 1.50 (br s, 2H,quin-CH₂), 2.34 (br s, 2H, quin-CH₂), 3.25 (q, J=7.2 Hz, 4H, ether),3.87 (br, s, 2H, quin-CH₂), 6.76 (br d, J=5.6 Hz, 1H, quin-CH) ppm

¹³C NMR (C₆D₆): δ 24.24, 28.54, 45.37, 65.95, 121.17, 125.34, 125.57,142.04, 163.09 (C═O) ppm

(ii) Preparation of8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline

The lithium carbamate compound prepared in Step (i) (8.47 g, 42.60 mmol)was put into a Schlenk flask. Subsequently, tetrahydrofuran (4.6 g, 63.9mmol) and 45 mL of diethyl ether were added in sequence. The Schlenkflask was immersed in a low-temperature bath at −20° C. formed ofacetone and a small amount of dry ice and stirred for 30 minutes, andthen t-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added thereto. At thistime, the color of the reaction mixture turned red. The mixture wasstirred for 6 hours while the temperature was maintained at −20° C. ACeCl₃.2LiCl solution (129 mL, 0.33 M, 42.60 mmol) dissolved intetrahydrofuran and tetramethylcyclopentinone (5.89 g, 42.60 mmol) weremixed in a syringe, and then charged into the flask under a nitrogenatmosphere. The temperature of the flask was slowly raised to roomtemperature. After 1 hour, a thermostat was removed, and a temperaturewas maintained at room temperature. Subsequently, water (15 mL) wasadded to the flask, and ethyl acetate was added thereto, followed byfiltration to obtain a filtrate. The filtrate was transferred to aseparatory funnel, followed by the addition of hydrochloric acid (2 N,80 mL) and shaking for 12 minutes. Then, a saturated aqueous solution ofsodium hydrogencarbonate (160 mL) was added thereto for neutralization,and then an organic layer was extracted. Anhydrous magnesium sulfate wasadded to the organic layer to remove moisture, followed by filtration,and the filtrate was taken to remove the solvent. The obtained filtratewas purified by column chromatography using hexane and ethyl acetate(v/v, 10:1) to obtain a yellow oil. The yield was 40%.

¹H NMR (C₆D₆): δ 1.00 (br d, 3H, Cp-CH₃), 1.63-1.73 (m, 2H, quin-CH₂),1.80 (s, 3H, Cp-CH₃), 1.81 (s, 3H, Cp-CH₃), 1.85 (s, 3H, Cp-CH₃), 2.64(t, J=6.0 Hz, 2H, quin-CH₂), 2.84-2.90 (br, 2H, quin-CH₂), 3.06 (br s,1H, Cp-H), 3.76 (br s, 1H, N—H), 6.77 (t, J=7.2 Hz, 1H, quin-CH), 6.92(d, J=2.4 Hz, 1H, quin-CH), 6.94 (d, J=2.4 Hz, 1H, quin-CH) ppm

(2) Preparation of[(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-eta5,kappa-N]titaniumdimethyl

(i) Preparation of[(1,2,3,4-tetrahydroquinoline-8-yl)tetramethylcyclopentadienyl-η5,κ-N]di-lithium Compound

In a dry box,8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline(8.07 g, 32.0 mmol) prepared in Step (1) and 140 mL of diethyl etherwere put into a round flask, a temperature was lowered to −30° C., andn-BuLi (17.7 g, 2.5 M, 64.0 mmol) was slowly added thereto whilestirring. The reaction was allowed to proceed for 6 hours while thetemperature was raised to room temperature. Thereafter, a solid wasobtained by filtration while washing with diethyl ether several times. Avacuum was applied to remove the remaining solvent to obtain adi-lithium compound (9.83 g) which is a yellow solid. The yield was 95%.

¹H NMR (C₆D₆, C₅D₅N): δ 2.38 (br s, 2H, quin-CH₂), 2.53 (br s, 12H,Cp-CH₃), 3.48 (br s, 2H, quin-CH₂), 4.19 (br s, 2H, quin-CH₂), 6.77 (t,J=6.8 Hz, 2H, quin-CH), 7.28 (br s, 1H, quin-CH), 7.75 (brs, 1H,quin-CH) ppm

(ii) Preparation of(1,2,3,4-tetrahydroquinoline-8-yl)tetramethylcyclopentadienyl-η5,κ-N]titaniumdimethyl

In a dry box, TiCl₄.DME (4.41 g, 15.76 mmol) and diethyl ether (150 mL)were put into a round flask, and MeLi (21.7 mL, 31.52 mmol, 1.4 M) wasslowly added thereto while stirring at −30° C. After stirring for 15minutes, the [(1,2,3,4-tetrahydroquinoline-8-yl)tetramethylcyclopentadienyl-η5, κ-N]di lithium compound prepared in Step(i) (5.30 g, 15.76 mmol) was placed in the flask. A mixture was stirredfor 3 hours while a temperature was raised to room temperature. Aftercompletion of the reaction, a vacuum was applied to remove the solvent,and the mixture was dissolved in pentane, and filtered to remove thefiltrate. A vacuum was applied to remove the pentane to obtain a darkbrown compound (3.70 g). The yield was 71.3%.

¹H NMR (C₆D₆): δ 0.59 (s, 6H, Ti—CH₃), 1.66 (s, 6H, Cp-CH₃), 1.69 (br t,J=6.4 Hz, 2H, quin-CH₂), 2.05 (s, 6H, Cp-CH₃), 2.47 (t, J=6.0 Hz, 2H,quin-CH₂), 4.53 (m, 2H, quin-CH₂), 6.84 (t, J=7.2 Hz, 1H, quin-CH), 6.93(d, J=7.6 Hz, quin-CH), 7.01 (d, J=6.8 Hz, quin-CH) ppm

¹³C NMR (C₆D₆): δ 12.12, 23.08, 27.30, 48.84, 51.01, 119.70, 119.96,120.95, 126.99, 128.73, 131.67, 136.21 ppm

Example 1

A 1.5 L autoclave continuous reactor was charged with a hexane solvent(5 kg/h) and 1-butene (1.2 kg/h), and then the temperature at the top ofthe reactor was preheated to 150° C. A triisobutyl aluminum compound(33.6 mmol/min), the transition metal compound 1 (0.3 μmol/min) obtainedin Preparation Example 1 as a catalyst, and a dimethylaniliniumtetrakis(pentafluorophenyl) borate cocatalyst (0.070 μmol/min) weresimultaneously introduced into the reactor. Subsequently, ethylene (0.87kg/h) was then charged into the autoclave reactor, and thecopolymerization reaction was continued at 150° C. for 30 minutes ormore in a continuous process at a pressure of 89 bar to obtain acopolymer. After drying for more than 12 hours, the physical propertieswere measured.

Examples 2 to 9

A copolymer was prepared in the same manner as in Example 1, except thatthe content of each substance was changed as shown in the followingTable 1.

Comparative Examples 1 to 3

A copolymer was prepared in the same manner as in Example 1, except thatthe transition metal compound 2 obtained in Preparation Example 2 wasused instead of the transition metal compound 1 as a catalyst, and thecontent of each substance was changed as shown in the following Table 1.

Comparative Examples 4 and 5

In Comparative Examples 4 and 5, LC170 and LC180 of LG Chem Ltd. werepurchased and used respectively.

TABLE 1 Reaction Catalyst Cocatalyst TiBAl Ethylene 1-butene 1-octenetemperture (μmol/min) (μmol/min) (mmol/min) (kg/h) (kg/h) (kg/h) (° C.)Example 1 0.30 0.90 0.070 0.87 1.20 — 185 Example 2 1.05 0.6 1.3 0.870.35 — 184 Example 3 0.75 0.6 1.05 0.87 0.25 — 156 Example 4 0.87 5.00.9 0.87 0.5 — 190 Example 5 0.25 0.75 0.05 0.87 1.2 — 194 Example 60.45 1.35 0.05 0.87 1.2 — 177 Example 7 0.33 0.99 0.05 0.87 1.2 — 185Example 8 0.30 0.90 0.070 0.87 — 1.00 175 Example 9 0.30 0.90 0.070 0.87— 1.40 182 Comparative 0.90 2.70 0.060 0.87 0.58 — 160 Example 1Comparative 1.95 0.06 0.85 0.87 0.65 — 170.3 Example 2 Comparative 1.560.6 0.65 0.87 0.52 — 145.8 Example 3

Experimental Example 1

The physical properties of the copolymers of Examples 1 to 9 andComparative Examples 1 to 5 were evaluated according to the followingmethods, and the results are shown in the following Table 2.

1) Density of Polymer

Measurement was performed in accordance with ASTM D-792.

2) Melt Index (MI) of Polymer

Measurement was performed in accordance with ASTM D-1238 [condition E,(190° C. and a load of 2.16 kg)].

3) Weight Average Molecular Weight (Mw, g/mol), Number Average MolecularWeight (Mn, g/mol), Z+1 Average Molecular Weight (Mz+1, g/mol) andMolecular Weight Distribution (MWD)

The weight average molecular weight (Mw, g/mol), the number averagemolecular weight (Mn, g/mol), and the Z+1 average molecular weight(Mz+1, g/mol) each were measured by gel permeation chromatography (GPC),and the molecular weight distribution was calculated by dividing theweight average molecular weight by the number average molecular weight.

Column: PL Olexis

Solvent: Trichlorobenzene (TCB)

Flow rate: 1.0 ml/min

Concentration of specimen: 1.0 mg/ml

Injection amount: 200 μl

Column temperature: 160° C.

Detector: Agilent High Temperature RI detector

Standard: Polystyrene (Calibration using cubic function)

4) 1-Octene and 1-Butene Content

1-Octene and 1-Butene content were measured by NMR. 1H-NMR was measuredat a condition of ns=16, d1=3s, solvent=TCE-d2, 373K, and then a TCE-d2solvent peak was corrected by 6.0 ppm. a peak of CH₃ of 1-butene at 0.92ppm and a peak relating to the CH₃ of 1-octene (triplet) at 0.96 ppmwere identified, and then the contents were calculated.

TABLE 2 Density (g/mL) MI (g/10 min) % [1-C8] (wt %) % [1-C4] (wt %) Mn(g/mol) Mw (g/mol) Mz + 1 (g/mol) MWD $\frac{Mn}{{Mz} + 1}*100$ Example1 0.868 3.6 — 27.3 37332 77074 234482 2.06 15.9 Example 2 0.863 5.7 —34.9 33336 69738 180383 2.09 18.5 Example 3 0.862 1.2 — 35.0 55426112552 331726 2.03 16.7 Example 4 0.867 8.1 — 29.6 30514 62633 1946682.05 15.7 Example 5 0.866 2.7 — 28.3 42308 86341 277895 2.04 15.2Example 6 0.860 14 — 32.4 26836 56456 172510 2.10 15.6 Example 7 0.8654.9 — 29.0 31241 69268 198930 2.22 15.7 Example 8 0.880 0.3 25.6 — 62617132916 411437 2.12 15.2 Example 9 0.869 1.4 31.5 — 52849 109583 3416202.07 15.5 Comparative 0.868 2.7 — 25.4 31157 72329 233025 2.32 13.4Example 1 Comparative 0.864 6.3 — 32.1 29090 66491 206247 2.29 14.1Example 2 Comparative 0.862 1.3 — 32.9 47691 106205 331126 2.23 14.4Example 3 Comparative 0.867 1.1 35.6 — 45295 104495 312682 2.31 14.5Example 4 Comparative 0.884 1.17 26.0 — 46222 108718 321910 2.35 14.4Example 5

Experimental Example 2

The tensile strengths of the copolymers of Examples 1 to 3 and 9, andComparative Examples 1 to 4 were measured in accordance with ASTM D-638.At this time, the test speed was 500 mm/min, and the average value wasmeasured 10 times per one specimen.

TABLE 3 Density (g/mL) MI (g/10 min) Mn (g/mol) Mw (g/mol) Mz + 1(g/mol) MWD $\frac{Mn}{{Mz} + 1}*100$ Example 1 0.868 3.6 37332 77074234482 2.06 15.9 Comparative 0.868 2.7 31157 72329 233025 2.32 13.4Example 1 Example 2 0.863 5.7 33336 69738 180383 2.09 18.5 Comparative0.864 6.3 29090 66491 206247 2.29 14.1 Example 2 Example 3 0.862 1.255426 112552 331726 2.03 16.7 Comparative 0.862 1.3 47691 106205 3311262.23 14.4 Example 3 Example 9 0.869 1.4 52849 109583 341620 2.07 15.5Comparative 0.867 1.1 45295 104495 312682 2.31 14.5 Example 4

In Table 3, Examples were paired with Comparative Examples in which thetype of comonomer, density and MI value were the same or similarrespectively, and then the tensile strengths were compared with eachother. Referring to Table 3 above, the copolymers of the Examples aremore resistant and have excellent a tensile strength when tensioned toelongate because the copolymers of the Examples are adjusted to have alarger Mw and Mz+1 than the copolymers of the Comparative Examples.

The invention claimed is:
 1. An olefin-based polymer, which has (1) adensity (d) ranging from 0.85 to 0.89 g/cc, measured according to ASTMD-792, (2) a melt index (MI) ranging from 0.1 g/10 min to 15 g/10 min,measured at 190° C., 2.16 kg load conditions, (3) a molecular weightdistribution (MWD) in a range of 1.0 to 3.0, and (4) a number averagemolecular weight (Mn) and a Z+1 average molecular weight (Mz+1)satisfying the following Equation 1:{Mn/(Mz+1)}×100>15,  [Equation 1] wherein the olefin-based polymer is acopolymer of ethylene and an alpha-olefin comonomer having 3 to 12carbon atoms.
 2. The olefin-based polymer according to claim 1, whereinthe olefin-based polymer has (5) a weight average molecular weight (Mw)in a range of 10,000 g/mol to 500,000 g/mol.
 3. The olefin-based polymeraccording to claim 1, wherein the olefin-based polymer has (6) a numberaverage molecular weight (Mn) in the range of 8,000 g/mol to 300,000g/mol.
 4. The olefin-based polymer according to claim 1, wherein theolefin-based polymer has (7) a Z+1 average molecular weight (Mz+1) in arange of 50,000 g/mol to 1,500,000 g/mol.
 5. The olefin-based polymeraccording to claim 1, wherein the olefin-based polymer has (7) a Z+1average molecular weight (Mz+1) in a range of 80,000 g/mol to 1,000,000g/mol.
 6. The olefin-based polymer according to claim 1, wherein theolefin-based polymer has (8) I₁₀/I₂>7.91(MI_(2.16))^(−0.188).
 7. Theolefin-based polymer according to claim 1, wherein the alpha-olefincomonomer includes any one or a mixture of two or more selected from thegroup consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene,1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene,1-tetradecene, 1-hexadecene, and 1-eicosene.
 8. The olefin-based polymeraccording to claim 1, wherein the alpha-olefin comonomer is comprised inan amount of from 5 wt % to 40 wt %, with respect to a total weight ofthe copolymer.
 9. The olefin-based polymer according to claim 1, whereinthe olefin-based polymer is obtained by a preparation method including astep of polymerizing an olefin-based monomer in the presence of acatalyst composition for olefin polymerization including a transitionmetal compound represented by the following Formula 1:

in Formula 1, R₁ is hydrogen; an alkyl having 1 to 20 carbon atoms; acycloalkyl having 3 to 20 carbon atoms; an alkenyl having 2 to 20 carbonatoms; an alkoxy having 1 to 20 carbon atoms; an aryl having 6 to 20carbon atoms; an arylalkoxy having 7 to 20 carbon atoms; an alkylarylhaving 7 to 20 carbon atoms; or an arylalkyl having 7 to 20 carbonatoms, R_(2a) to R_(2e) each independently represent hydrogen; ahalogen; an alkyl having 1 to 20 carbon atoms; a cycloalkyl having 3 to20 carbon atoms; an alkenyl having 2 to 20 carbon atoms; an alkoxyhaving 1 to 20 carbon atoms; or an aryl having 6 to 20 carbon atoms, R₃is hydrogen; a halogen; an alkyl having 1 to 20 carbon atoms; acycloalkyl having 3 to 20 carbon atoms; an alkenyl having 2 to 20 carbonatoms; an aryl having 6 to 20 carbon atoms; an alkylaryl having 7 to 20carbon atoms; an arylalkyl having 7 to 20 carbon atoms; an alkylamidohaving 1 to 20 carbon atoms; an arylamido having 6 to 20 carbon atoms;an alkylidene having 1 to 20 carbon atoms; or phenyl substituted withone or more selected from the group consisting of a halogen, an alkylhaving 1 to 20 carbon atoms, a cycloalkyl having 3 to 20 carbon atoms,an alkenyl having 2 to 20 carbon atoms, an alkoxy having 1 to 20 carbonatoms, and an aryl having 6 to 20 carbon atoms, R₄ to R₉ eachindependently represent hydrogen; a silyl; an alkyl having 1 to 20carbon atoms; a cycloalkyl having 3 to 20 carbon atoms; an alkenylhaving 2 to 20 carbon atoms; an aryl having 6 to 20 carbon atoms; analkylaryl having 7 to 20 carbon atoms; an arylalkyl having 7 to 20carbon atoms; or a metalloid radical of a Group 14 metal substitutedwith a hydrocarbyl having 1 to 20 carbon atoms; and two or more adjacentones of R₆ to R₉ are optionally connected to each other to form analiphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6to 20 carbon atoms, wherein the aliphatic ring or aromatic ring isoptionally substituted with a halogen, an alkyl having 1 to 20 carbonatoms, an alkenyl having 2 to 12 carbon atoms, or an aryl having 6 to 12carbon atoms Q is Si, or C, M is a Group 4 transition metal, X₁ and X₂are each independently hydrogen; a halogen; an alkyl having 1 to 20carbon atoms; a cycloalkyl having 3 to 20 carbon atoms; an alkenylhaving 2 to 20 carbon atoms; an aryl having 6 to 20 carbon atoms; analkylaryl having 7 to 20 carbon atoms; an arylalkyl having 7 to 20carbon atoms; an alkylamino having 1 to 20 carbon atoms; an arylaminohaving 6 to 20 carbon atoms; or an alkylidene having 1 to 20 carbonatoms.
 10. The olefin-based polymer according to claim 9, wherein inFormula 1, R₁ is hydrogen or an alkyl having 1 to 12 carbon atoms,R_(2a) to R_(2e) each independently represent hydrogen; an alkyl having1 to 12 carbon atoms; or an alkoxy having 1 to 12 carbon atoms, R₃ ishydrogen; an alkyl having 1 to 12 carbon atoms; or phenyl, R₄ and R₅each independently represent hydrogen; or an alkyl having 1 to 12 carbonatoms, R₆ to R₉ each independently represent hydrogen or methyl, Q isSi, M is Ti, and X₁ and X₂ each independently represent hydrogen or analkyl having 1 to 12 carbon atoms.
 11. The olefin-based polymeraccording to claim 9, wherein the transition metal compound of Formula 1comprises a compound represented by any one among the structures below:


12. The olefin-based polymer according to claim 9, wherein the catalystcomposition further includes one or more cocatalyst compoundsrepresented by the following Formula 8, Formula 9 or Formula 10,—[Al(R₁₁)—O]_(a)—,  [Formula 8]A(R₁₁)₃,  [Formula 9][L-H]⁺[W(D)₄]⁻ or [L]⁺[W(D)₄]⁻,  [Formula 10] in Formulas 8 to 10, R₁₁is the same or different, and each independently selected from the groupconsisting of a halogen, a hydrocarbyl having 1 to 20 carbon atoms, anda hydrocarbyl having 1 to 20 carbon atoms substituted with a halogen, Ais aluminum or boron, D is independently an aryl having 6 to 20 carbonatoms or an alkyl having 1 to 20 carbon atoms in which at least onehydrogen atom is substituted with a substituent selected from the groupconsisting of a halogen, a hydrocarbyl having 1 to 20 carbon atoms, analkoxy having 1 to 20 carbon atoms, and an aryloxy having 6 to 20 carbonatoms, H is a hydrogen atom, L is a neutral Lewis base and [L-H]⁺ is aconjugated acid cation in [L-H]⁺[W(D)₄]⁻, and [L]⁺ is a Lewis acid in[L]⁺[W(D)₄]⁻, W is a Group 13 element, and a is an integer of 2 or more.13. The olefin-based polymer according to claim 9, wherein thepolymerization of the olefin-based monomer is carried out at atemperature of about 25° C. to about 500° C., and a pressure of about 1kgf/cm² to about 100 kgf/cm².